CN111757897B

CN111757897B - Copolymer and colored resin composition

Info

Publication number: CN111757897B
Application number: CN201980014495.4A
Authority: CN
Inventors: 河西裕
Original assignee: Sumitomo Chemical Co Ltd
Current assignee: Sumitomo Chemical Co Ltd
Priority date: 2018-02-26
Filing date: 2019-02-19
Publication date: 2022-09-16
Anticipated expiration: 2039-02-19
Also published as: US20210047449A1; JP2019147949A; TW201938608A; US11485810B2; KR20200125636A; CN111757897A; WO2019163734A1

Abstract

The invention provides a copolymer useful as a blending component of a colored resin composition capable of producing a coating film and a color filter with excellent solvent resistance. The copolymer is characterized by comprising a structural unit (Aa) derived from an aromatic carboxylic acid having an ethylenically unsaturated bond, a structural unit (Ab) represented by formula (Z), and a structural unit (Ac) derived from an unsaturated compound having a cyclic ether structure having 2-4 carbon atoms. [ in the formula (Z), L represents a single bond or a 2-valent linking group, A represents a phenyl group which may have a substituent other than a carboxyl group or a naphthyl group which may have a substituent other than a carboxyl group, and R ^a Represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, wherein the hydrogen atom contained in the alkyl group may be substituted with a hydroxyl group]。

Description

Copolymer and colored resin composition

Technical Field

The present invention relates to a copolymer and a colored resin composition containing the copolymer, and also relates to a color filter formed from the colored resin composition.

Background

Various dyes are known as colorants contained in colored resin compositions for forming color filters included in liquid crystal display devices, solid-state imaging elements, and the like. Patent document 1 describes that a squaric acid is contained

Colored tree of dyesA fat composition.

Documents of the prior art

Patent document

Patent document 1: japanese laid-open patent publication No. 2015-86379

Disclosure of Invention

The invention aims to provide a color filter with excellent solvent resistance compared with a color filter formed by a conventional colored resin composition, a colored resin composition capable of manufacturing the color filter and a copolymer contained in the colored resin composition.

The present invention provides the following [1] to [6 ].

[1] A copolymer contains a structural unit (Aa) derived from an aromatic carboxylic acid having an ethylenically unsaturated bond, a structural unit (Ab) represented by the formula (Z), and a structural unit (Ac) derived from an unsaturated compound having a cyclic ether structure having 2 to 4 carbon atoms.

[ in the formula (Z), L represents a single bond or a 2-valent linking group, A represents a phenyl group which may have a substituent other than a carboxyl group or a naphthyl group which may have a substituent other than a carboxyl group, and R ^a Represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and the hydrogen atom contained in the alkyl group may be substituted with a hydroxyl group.]

[2] The copolymer according to [1], wherein the total content of the structural unit (Aa) and the structural unit (Ab) is 40 to 90 mol% based on the total amount of all the structural units.

[3] A colored resin composition comprising the copolymer according to [1] or [2] and a colorant.

[4]According to [3]]The colored resin composition, wherein the colorant comprises a1 st dye, and the 1 st dye is a squaric acid

A dye.

[5] A cured film formed from the colored resin composition according to [3] or [4 ].

[6] A color filter formed from the colored resin composition according to [3] or [4 ].

According to the copolymer of the present invention, a color filter having excellent solvent resistance can be produced.

Detailed Description

[ copolymer ]

The copolymer contains a structural unit (Aa) derived from an aromatic carboxylic acid having an ethylenically unsaturated bond, a structural unit (Ab) represented by the formula (Z), and a structural unit (Ac) derived from an unsaturated compound having a cyclic ether structure having 2-4 carbon atoms.

The copolymer (a) of the present invention may further contain a structural unit (Aa), a structural unit (Ab), and a structural unit other than the structural unit (Ac) (hereinafter, also referred to as "structural unit (Ad)").

< structural Unit (Aa) >

The structural unit (Aa) derived from an aromatic carboxylic acid having an ethylenically unsaturated bond is a structural unit derived from at least one compound (hereinafter, also referred to as "compound (Aa)") selected from an aromatic carboxylic acid having an ethylenically unsaturated bond and an aromatic carboxylic anhydride having an ethylenically unsaturated bond. The structural unit (Aa) can be obtained by synthesizing a copolymer using the compound (Aa) as a monomer. Alternatively, the compound may be obtained by reacting a compound (Aa ') having an aromatic carboxylic acid with another structural unit (Aa').

Specific examples of the compound (Aa) include aromatic carboxylic acids such as o-vinylbenzoic acid, m-vinylbenzoic acid, p-vinylbenzoic acid, 3-vinylphthalic acid, and 4-vinylphthalic acid; aromatic carboxylic acid anhydrides such as 3-vinylphthalic anhydride and 4-vinylphthalic anhydride.

< structural Unit (Ab) >)

The structural unit (Ab) represented by the formula (Z) can be obtained by polymerizing a compound represented by the formula (Z') (hereinafter, also referred to as "compound (Ab)") as a monomer. Alternatively, it can be obtained by reacting a compound having-L-A (Ab ') with another structural unit (Ab').

In the formula (Z'), L, A and R ^a The same as in the formula (Z).

L in the formulae (Z) and (Z') represents a single bond or a linking group having a valence of 2, and examples of the linking group having a valence of 2 include a hydrocarbon group having a valence of 2 and having 1 to 20 carbon atoms, and-CH contained in the hydrocarbon group ₂ -may be substituted by-COO-, -O-, -CO-, -NH-, -NHCO-, -CONH-, -NHCOO-, -OCONH-. As the linking group having a valence of 2, preferred is-CH ₂ －、－COO－、－O－、－NHCO－、－CONH－、－NHCOO－、－OCONH－。

A in the formulae (Z) and (Z') represents a phenyl group or a naphthyl group which may have a substituent other than a carboxyl group. Examples of the substituent that A may have include a hydroxyl group, an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, a phenyl group which may have a substituent, an alicyclic hydrocarbon group having 3 to 12 carbon atoms, and a combination thereof.

Examples of the alkyl group having 1 to 12 carbon atoms include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, an undecyl group, and a dodecyl group.

Examples of the alkoxy group having 1 to 12 carbon atoms include a methoxy group, an ethoxy group, a propoxy group, a butoxy group, a pentyloxy group, a hexyloxy group, an octyloxy group, a 2-ethylhexyloxy group, a nonyloxy group, a decyloxy group, an undecyloxy group, a dodecyloxy group, and the like.

Examples of the alicyclic hydrocarbon group having 3 to 12 carbon atoms include the following groups. Is a bonding site to the loop.

Among these substituents, a hydroxyl group, an alkyl group having 1 to 12 carbon atoms, or an alkoxy group having 1 to 12 carbon atoms is preferable, a hydroxyl group or an alkyl group having 1 to 12 carbon atoms is more preferable, an alkyl group having 1 to 12 carbon atoms is further preferable, and an alkyl group having 1 to 6 carbon atoms is further more preferable.

R of formula (Z) and formula (Z') ^a Represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and the hydrogen atom contained in the alkyl group may be substituted with a hydroxyl group.

Examples of the alkyl group having 1 to 4 carbon atoms include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, and a tert-butyl group.

Examples of the alkyl group in which a hydrogen atom is substituted with a hydroxyl group include a hydroxymethyl group, a 1-hydroxyethyl group, a 2-hydroxyethyl group, a 1-hydroxypropyl group, a 2-hydroxypropyl group, a 3-hydroxypropyl group, a 1-hydroxy-1-methylethyl group, a 2-hydroxy-1-methylethyl group, a 1-hydroxybutyl group, a 2-hydroxybutyl group, a 3-hydroxybutyl group, and a 4-hydroxybutyl group.

As R ^a Preferred examples thereof include a hydrogen atom, a methyl group, a hydroxymethyl group, a 1-hydroxyethyl group and a 2-hydroxyethyl group, and more preferred examples thereof include a hydrogen atom and a methyl group.

Examples of the compound represented by the formula (Z') include compounds represented by the following formulae (Z-1), (Z-2), (Z-3), (Z-4), (Z-5) and (Z-6).

< structural Unit (Ac) >

The structural unit (Ac) derived from an unsaturated compound having a cyclic ether structure having 2 to 4 carbon atoms can be obtained by synthesizing a copolymer using, as a monomer, an unsaturated compound having a cyclic ether structure having 2 to 4 carbon atoms (hereinafter, also referred to as "compound (Ac)"). Alternatively, the compound (Ac ') may be obtained by reacting a compound (Ac ') having a cyclic ether structure having 2 to 4 carbon atoms with another structural unit (Ac ').

The compound (Ac) is an unsaturated compound having a cyclic ether structure having 2 to 4 carbon atoms (for example, at least one selected from the group consisting of an oxirane ring, an oxetane ring, and a tetrahydrofuran ring). Examples of the compound (Ac) include a compound having an oxirane group and an ethylenically unsaturated bond (Ac1), a compound having an oxetanyl group and an ethylenically unsaturated bond (Ac2), and a compound having a tetrahydrofuranyl group and an ethylenically unsaturated bond (Ac 3).

Examples of the compound (Ac1) include a compound (Ac 1-1) having a structure obtained by epoxidizing a linear or branched unsaturated aliphatic hydrocarbon and a compound (Ac 1-2) having a structure obtained by epoxidizing an unsaturated alicyclic hydrocarbon. The compound for deriving the structural unit (Ac) is preferably the compound (Ac1) in view of further improving the reliability of the obtained film, such as heat resistance and chemical resistance. Further, the monomer (Ac 1-2) is more preferable in terms of excellent storage stability of the copolymer.

Examples of the compound (Ac 1-1) include glycidyl (meth) acrylate, β -methylglycidyl (meth) acrylate, β -ethylglycidyl (meth) acrylate, glycidyl vinyl ether, o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, p-vinylbenzyl glycidyl ether, α -methyl-o-vinylbenzyl glycidyl ether, α -methyl-m-vinylbenzyl glycidyl ether, α -methyl-p-vinylbenzyl glycidyl ether, 2, 3-bis (glycidoxymethyl) styrene, 2, 4-bis (glycidoxymethyl) styrene, 2, 5-bis (glycidoxymethyl) styrene, 2, 6-bis (glycidoxymethyl) styrene, 2,3, 4-tris (glycidoxymethyl) styrene, 2,3, 5-tris (glycidoxymethyl) styrene, 2,3, 6-tris (glycidoxymethyl) styrene, 3,4, 5-tris (glycidoxymethyl) styrene, 2,4, 6-tris (glycidoxymethyl) styrene and the like.

Examples of the compound (Ac 1-2) include vinylcyclohexene monooxide, 1, 2-epoxy-4-vinylcyclohexane (for example, Celloxide 2000; manufactured by Daicel corporation), 3, 4-epoxycyclohexylmethyl (meth) acrylate (for example, Cyclomer A400; manufactured by Daicel corporation), 3, 4-epoxycyclohexylmethyl (meth) acrylate (for example, Cyclomer) M100; manufactured by Daicel corporation), a compound represented by the formula (I), a compound represented by the formula (II), and the like.

[ formula (I) and formula (II) wherein R ^b1 And R ^b2 Represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and the hydrogen atom contained in the alkyl group may be substituted with a hydroxyl group.

X ^b1 And X ^b2 Represents a single bond, — R ^b3 －、*－R ^b3 －O－、*－R ^b3 -S-or R ^b3 －NH－。

R ^b3 Represents an alkanediyl group having 1 to 6 carbon atoms.

Denotes the bonding site to O. ]

As R ^b1 And R ^b2 Preferred examples thereof include a hydrogen atom, a methyl group, a hydroxymethyl group, a 1-hydroxyethyl group and a 2-hydroxyethyl group, and more preferred examples thereof include a hydrogen atom and a methyl group.

Examples of the alkanediyl group include a methylene group, an ethylene group, a propane-1, 2-diyl group, a propane-1, 3-diyl group, a butane-1, 4-diyl group, a pentane-1, 5-diyl group, and a hexane-1, 6-diyl group.

As X ^b1 And X ^b2 Preferred examples thereof include a single bond, methylene, ethylene and-CH ₂ －O－、*－CH ₂ CH ₂ -O-, and more preferably a single bond or-CH ₂ CH ₂ -O-. Denotes the bonding site to O.

The compound represented by the formula (I) includes a compound represented by any one of the formulae (I-1) to (I-15), preferably a compound represented by the formula (I-1), the formula (I-3), the formula (I-5), the formula (I-7), the formula (I-9) or the formulae (I-11) to (I-15), and more preferably a compound represented by the formula (I-1), the formula (I-7), the formula (I-9) or the formula (I-15).

The compound represented by the formula (II) includes a compound represented by any one of the formulae (II-1) to (II-15), preferably a compound represented by the formula (II-1), the formula (II-3), the formula (II-5), the formula (II-7), the formula (II-9) or the formulae (II-11) to (II-15), and more preferably a compound represented by the formula (II-1), the formula (II-7), the formula (II-9) or the formula (II-15).

The compound represented by the formula (I) and the compound represented by the formula (II) may be used alone or in combination of 2 or more. When they are used in combination, the content ratio [ the compound represented by the formula (I): the compound represented by the formula (II) is preferably 5: 95-95: 5, more preferably 20: 80-80: 20. for example, a 50: 50 contains a mixture of the compound represented by the formula (I-1) and the compound represented by the formula (II-1).

The compound (Ac2) is more preferably a compound having an oxetanyl group and a (meth) acryloyloxy group. Examples of the compound (Ac2) include 3-methyl-3-methacryloxymethyloxetane, 3-methyl-3-acryloxymethyloxetane, 3-ethyl-3-methacryloxymethyloxetane, 3-ethyl-3-acryloxymethyloxetane, 3-methyl-3-methacryloxyethyloxetane, 3-methyl-3-acryloxyethyloxetane, 3-ethyl-3-methacryloxyethyloxetane, and 3-ethyl-3-acryloxyethyloxetane.

The compound (Ac3) is preferably a compound having a tetrahydrofuranyl group and a (meth) acryloyloxy group. Examples of the compound (Ac3) include tetrahydrofurfuryl acrylate (e.g., Biscoat V #150, manufactured by osaka organic chemical industries, inc.), tetrahydrofurfuryl methacrylate, and the like.

The structural unit (Ac) is preferably a structural unit represented by the formula (Ac-1) or (Ac-2) in view of excellent storage stability of the copolymer, chemical resistance, heat resistance and mechanical strength of the obtained film. The structural unit represented by the formula (Ac-1) is derived from the compound represented by the formula (I), and the structural unit represented by the formula (Ac-2) is derived from the compound represented by the formula (II).

[ in the formulae (Ac-1) and (Ac-2), R ^b1 And R ^b2 Represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and the hydrogen atom contained in the alkyl group may be substituted with a hydroxyl group.

R ^b3 Represents an alkanediyl group having 1 to 6 carbon atoms.

Denotes the bonding site to O. ]

< structural Unit (Ad) >

Examples of the structural unit (Ad) include a structural unit which can be obtained by synthesizing a copolymer using the following compound (Ad) as a monomer.

Examples of the compound (Ad) include methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, sec-butyl (meth) acrylate, tert-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, dodecyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, cyclopentyl (meth) acrylate, cyclohexyl (meth) acrylate, 2-methylcyclohexyl (meth) acrylate, and tricyclo [5.2.1.0 ] meth) acrylate ^2,6 ]Decan-8-yl ester (which is known as "dicyclopentyl (meth) acrylate" as a common name in the art, and may be referred to as "tricyclodecanyl (meth) acrylate"), (meth) acrylic acid tricyclo [5.2.1.0 ] ^2,6 ]Decen-8-yl ester (commonly known in the art as "dicyclopentenyl (meth) acrylate"), (meth) acrylic acid esters such as dicyclopentenyloxyethyl (meth) acrylate, isobornyl (meth) acrylate, adamantyl (meth) acrylate, allyl (meth) acrylate, and propargyl (meth) acrylate;

hydroxyl group-containing (meth) acrylates such as 2-hydroxyethyl (meth) acrylate and 2-hydroxypropyl (meth) acrylate;

dicarboxylic acid diesters such as diethyl maleate, diethyl fumarate and diethyl itaconate;

bicyclo [2.2.1] hept-2-ene, 5-methylbicyclo [2.2.1] hept-2-ene, 5-ethylbicyclo [2.2.1] hept-2-ene, 5-hydroxybicyclo [2.2.1] hept-2-ene, 5-hydroxymethylbicyclo [2.2.1] hept-2-ene, 5- (2 '-hydroxyethyl) bicyclo [2.2.1] hept-2-ene, 5-methoxybicyclo [2.2.1] hept-2-ene, 5-ethoxybicyclo [2.2.1] hept-2-ene, 5, 6-dihydroxybicyclo [2.2.1] hept-2-ene, 5, 6-bis (hydroxymethyl) bicyclo [2.2.1] hept-2-ene, 5, 6-bis (2' -hydroxyethyl) bicyclo [2.2.1] hept-2-ene, 5, 6-dimethoxybicyclo [ 2.1] hept-2-ene, 5, 6-bis (2.1) hept-2-ene, 5-hydroxybicyclo [2.2.1] hept-2-ene, 5-hydroxyhept-2-ene, 5-hydroxybicyclo [2.2.1] hept-2-ene, 5-2.1 ] hept-2-ene, 5-hydroxy-2-hydroxy-2-hydroxy-1-2-hydroxy-2-1-hydroxy-2-hydroxy-2-1-2-ethyl-2-ene, 5-hydroxy-2-hydroxy-2, 5, 6-2-hydroxy-2-one, 5-2-one, 5, 6-one, 2-one, 2-one, 5, Bicyclic unsaturated compounds such as 5-hydroxymethyl-5-methylbicyclo [2.2.1] hept-2-ene, 5-tert-butoxycarbonylbicyclo [2.2.1] hept-2-ene, 5-cyclohexyloxycarbonybicyclo [2.2.1] hept-2-ene, 5-phenoxycarbonylbicyclo [2.2.1] hept-2-ene, 5, 6-bis (tert-butoxycarbonyl) bicyclo [2.2.1] hept-2-ene and 5, 6-bis (cyclohexyloxycarbonyl) bicyclo [2.2.1] hept-2-ene;

dicarbonylimide derivatives such as N-phenylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide, N-succinimidyl-3-maleimidobenzoate, N-succinimidyl-4-maleimidobutyrate, N-succinimidyl-6-maleimidocaproate, N-succinimidyl-3-maleimidopropionate and N- (9-acridinyl) maleimide;

styrene, α -methylstyrene, m-methylstyrene, p-methylstyrene, vinyltoluenes, p-methoxystyrene, acrylonitrile, methacrylonitrile, vinyl chloride, vinylidene chloride, acrylamide, methacrylamide, vinyl acetate, 1, 3-butadiene, isoprene, 2, 3-dimethyl-1, 3-butadiene and the like.

Among these, styrene, vinyltoluene, N-phenylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide, bicyclo [2.2.1] hept-2-ene and the like are preferable from the viewpoint of copolymerization reactivity and heat resistance.

< ratio of each structural unit >

The copolymer (A) is, for example, the following copolymer [ K1] or copolymer [ K2 ].

Copolymer [ K1 ]: a copolymer of the compound (Aa), the compound (Ab) and the compound (Ac);

copolymer [ K2 ]: a copolymer of the compound (Aa), the compound (Ab), the compound (Ac) and the compound (Ad).

In the copolymer [ K1], the ratio of each structural unit to the total structural units constituting the copolymer [ K1] is preferably

Structural unit from compound (Aa): 5 to 40 mol%,

Structural unit from compound (Ab): 5 to 90 mol%,

Structural unit from compound (Ac): 5 to 40 mol% of a surfactant,

more preferably

Structural unit from compound (Aa): 10 to 35 mol%,

Structural unit from compound (Ab): 10 to 80 mol%,

Structural unit from compound (Ac): 10 to 35 mol%.

When the ratio of the structural units constituting the copolymer [ K1] is within the above range, the solvent resistance of a coating film obtained from the copolymer-containing colored resin composition tends to be excellent.

The copolymer [ K1] can be produced, for example, by a method described in "Experimental method for Polymer Synthesis" (Otsu Hiroshima, Prossum: Kagaku K.K., 1 st edition, 1 st printing, 3/1/1972) and a literature cited therein.

Specifically, predetermined amounts of the compound (Aa), the compound (Ab), the compound (Ac), a polymerization initiator, a solvent and the like are placed in a reaction vessel, and oxygen is replaced with nitrogen gas, for example, to form a deoxygenated atmosphere, and heating and heat-holding are performed while stirring. The polymerization initiator and the solvent used herein are not particularly limited, and polymerization initiators and solvents generally used in this field can be used. Examples of the polymerization initiator include azo compounds (e.g., 2 '-azobisisobutyronitrile, 2' -azobis (2, 4-dimethylvaleronitrile), and organic peroxides (e.g., benzoyl peroxide), and examples of the solvent include solvents that dissolve the monomers, and solvents described below used in the colored resin composition.

The copolymer obtained by the above method may be used as it is as a solution after the reaction, may be used as a concentrated or diluted solution, or may be used as a solid (powder) taken out as a solid (powder) by a method such as reprecipitation. In particular, by using the solvent used in the colored resin composition of the present invention as a polymerization solvent, the solution after the reaction can be used as it is for the production of the colored resin composition, and therefore, the production process of the colored resin composition can be simplified.

In the copolymer [ K2], the ratio of each structural unit to the total structural units constituting the copolymer [ K2] is preferably

Structural unit from compound (Aa): 5 to 40 mol%,

Structural unit from compound (Ab): 5 to 90 mol%,

Structural unit from compound (Ac): 5 to 40 mol%,

Structural units from compound (Ad): 1 to 40 mol% of a surfactant,

more preferably

Structural unit from compound (Aa): 10 to 35 mol%,

Structural unit from compound (Ab): 10 to 80 mol%,

Structural unit from compound (Ac): 10 to 35 mol%,

Structural units from compound (Ad): 5 to 35 mol%.

When the ratio of the structural units of the copolymer [ K2] is within the above range, the solvent resistance of a coating film obtained from the copolymer-containing colored resin composition tends to be excellent. The resin [ K2] can be produced by the same method as that for the resin [ K1 ].

Examples of the copolymer [ K1] include copolymers represented by the formula 50: 50 a copolymer containing a mixture of p-vinylbenzoic acid/the compound represented by the formula (Z-1)/the compound represented by the formula (I-1) and the compound represented by the formula (II-1), in an amount of 50: 50 a copolymer containing a mixture of p-vinylbenzoic acid/the compound represented by the formula (Z-2)/the compound represented by the formula (I-1) and the compound represented by the formula (II-1), and the like.

Examples of the copolymer [ K2] include those in which the above-exemplified resin [ K1] further contains a structural unit derived from the compound (Ad).

The weight average molecular weight (Mw) of the copolymer (a) in terms of polystyrene is preferably 3000 to 100000, more preferably 5000 to 50000, still more preferably 5000 to 20000, and particularly preferably 5000 to 10000. When the weight average molecular weight (Mw) of the copolymer (a) is within the above range, the coating property of the resin composition tends to be good.

The dispersity [ weight average molecular weight (Mw)/number average molecular weight (Mn) ] of the copolymer (A) is preferably 1.1 to 6.0, more preferably 1.2 to 4.0. If the degree of dispersion is within the above range, the solvent resistance of the resulting coating film tends to be excellent.

The acid value of the copolymer (A) is preferably 1 mg-KOH/g to 180 mg-KOH/g, more preferably 5 mg-KOH/g to 150 mg-KOH/g, and still more preferably 10 mg-KOH/g to 135 mg-KOH/g. Here, the acid value is a value measured as the amount (mg) of potassium hydroxide required for neutralizing 1g of the resin, and can be determined by titration using an aqueous potassium hydroxide solution. When the acid value of the copolymer (A) is within the above range, the resulting coating film tends to have excellent adhesion to a substrate.

In addition, the total content of the structural unit (Aa) and the structural unit (Ab) in the copolymer (A) is preferably 40 to 90 mol% based on the total amount of all the structural units constituting the copolymer (A).

[ colored resin composition ]

The colored resin composition of the present invention contains the copolymer (a), the colorant (B), and the solvent (E), and may contain at least one selected from the polymerizable compound (C) and the polymerization initiator (D). The colored resin composition of the present invention may contain a polymerization initiator (D1) and a leveling agent (F) as required. The details of each component will be described below. In the present specification, unless otherwise specified, a plurality of compounds exemplified as the respective components may be used alone or in combination.

< copolymer (A) >

The copolymer (A) is as described above. The content of the copolymer (a) is preferably 30 to 90% by mass, more preferably 35 to 80% by mass, and still more preferably 40 to 70% by mass, based on the solid content of the colored resin composition of the present invention. When the content of the copolymer (a) is within the above range, the obtained coating film tends to have excellent heat resistance and excellent adhesion to a substrate and chemical resistance. Here, the solid content of the colored resin composition means an amount obtained by removing the content of the solvent (E) from the total amount of the colored resin composition of the present invention.

< colorant (B) >)

The colorant (B) contains a dye. The colorant (B) preferably contains the 1 st dye (B-1) described in detail below. This is because when the colorant (B) contains the 1 st dye (B-1), the solvent resistance of the coating film obtained from the colored resin composition tends to be lowered, and therefore the effect of the present invention of obtaining excellent solvent resistance becomes more remarkable. The colorant (B) may also contain, as a dye, a2 nd dye (B-2) different from the 1 st dye (B-1) together with the 1 st dye (B-1), and may also contain only the 2 nd dye (B-2).

(dye No. 1 (B-1))

The 1 st dye (B-1) is a squaric acid

A dye. As squaric acid

The dye is not particularly limited as long as it is a compound represented by the formula (III).

In the formula (III), A and A' each independently represent an organic group containing an aromatic ring or a heterocyclic ring. The compound represented by the formula (III) also includes compounds having all resonance structures that are possible with respect to the structure represented by the formula (III).

As the squaric acid of formula (III)

Examples of the dye include compounds described in Japanese patent application laid-open No. 2013-76926. As squaric acid

Among the dyes, the compounds of the formula (III) are also preferredIs a compound represented by the formula (IV) (hereinafter, sometimes referred to as "compound (IV)").

In the formula (IV), R ¹ ～R ⁴ Each independently represents a hydrogen atom, a halogen atom, a hydroxyl group or a 1-valent saturated hydrocarbon group having 1 to 20 carbon atoms. The hydrogen atom or methyl group contained in the saturated hydrocarbon group having a valence of 1 may be substituted with a halogen atom, a hydroxyl group or an alkylamino group having 1 to 8 carbon atoms, and an oxygen atom or a sulfur atom may be inserted between the carbon atoms constituting the saturated hydrocarbon group having a valence of 1.

R ⁵ ～R ⁸ Independently of one another, represents a hydrogen atom or a hydroxyl group.

Ar ¹ And Ar ² Each independently represents a group represented by the following formula (i).

In the formula (i), R ¹² Represents a C1-valent saturated hydrocarbon group having 1 to 20 carbon atoms or a C2-20-valent unsaturated hydrocarbon group having 1 to 20 carbon atoms, and m represents an integer of 1 to 5. When m is 2 or more, plural R ¹² May be the same or different. Denotes the bonding site to the nitrogen atom.

R ⁹ And R ¹⁰ Each independently represents a 1-valent saturated hydrocarbon group having 1 to 20 carbon atoms or a group represented by the formula (i). The hydrogen atom or methyl group contained in the saturated hydrocarbon group having a valence of 1 may be substituted with a halogen atom, a hydroxyl group, or an amino group substituted with 1 or 2 alkyl groups having 1 to 8 carbon atoms, and an oxygen atom or a sulfur atom may be inserted between the carbon atoms constituting the saturated hydrocarbon group having a valence of 1.

In the formula (II), as R ¹ ～R ⁴ Examples of the halogen atom in (2) include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.

As R ¹ ～R ⁴ 、R ⁹ 、R ¹⁰ And R ¹² Carbon atom of (1)The number of the saturated hydrocarbon groups having a valence of 1 to 20 as a sub-group is, for example, a linear alkyl group having 1 to 20 carbon atoms such as a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, a dodecyl group, a hexadecyl group and an eicosyl group; a branched alkyl group having 3 to 20 carbon atoms such as an isopropyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, an isopentyl group, a neopentyl group, and a 2-ethylhexyl group; and (c) 3-20 alicyclic saturated hydrocarbon groups such as cyclopropyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, and tricyclodecyl.

Examples of the group in which a hydrogen atom or a methyl group contained in these saturated hydrocarbon groups is substituted with a halogen atom, a hydroxyl group, or an amino group substituted with 1 or 2 alkyl groups having 1 to 8 carbon atoms include groups represented by the following formulae. Examples of the amino group substituted with 1 or 2 alkyl groups having 1 to 8 carbon atoms include a methylamino group, an ethylamino group, an n-propylamino group, an n-butylamino group, an n-pentylamino group, a dimethylamino group, a diethylamino group, a dibutylamino group, a methylethylamino group, and the like. In the following formulae, a represents a bonding site.

Examples of the group having an oxygen atom or a sulfur atom inserted between carbon atoms constituting these saturated carbon groups include groups represented by the following formulae. In the following formulae, a indicates a bonding site.

As R ¹² Examples of the 1-valent unsaturated hydrocarbon group having 2 to 20 carbon atoms in the (a) include a vinyl group, a propenyl group, a butenyl group, a pentenyl group, a hexenyl group, a heptenyl group, an octenyl group, a nonenyl group, and a decenyl group.

Examples of the group represented by the formula (i) include the following groups. Denotes the bonding site to the nitrogen atom.

As R ¹ ～R ⁴ Preferred are a hydrogen atom, a hydroxyl group and a methyl group, and more preferred is a hydrogen atom.

As R ⁹ And R ¹⁰ Preferably octyl, nonyl, decyl, dodecyl, 2-ethylhexyl and a group of the formula (i), more preferably 2-ethylhexyl.

As R ¹² The alkyl group having 1 to 4 carbon atoms is preferable, and the methyl group and the ethyl group are more preferable.

In the formula (IV), in

The radicals indicated are set to X ¹ Will be

The radicals indicated are set to X ² When is taken as X ¹ And X ² Examples of the group represented by the formula (A2-1) to (A2-7) include groups represented by the formula (A2-1). Denotes the bonding site to a carbon atom.

Examples of the compound represented by the formula (IV) include compounds (AII-1) to (AII-21) shown in Table 1.

[ Table 1]

Compound (I)

R ¹

R ²

R ³

R ⁴

R ⁵

R ⁶

R ⁷

R ⁸

X ¹

X ²

AII-1

H

A2-1

AII-2

H

A2-2

AII-3

H

A2-3

AII-4

H

A2-4

AII-5

H

A2-5

AII-6

H

A2-6

AII-7

H

A2-7

AII-8

H

OH

H

A2-1

AII-9

H

OH

H

A2-2

AII-10

H

OH

H

A2-3

AII-11

H

OH

H

A2-4

AII-12

H

OH

H

A2-5

AII-13

H

OH

H

A2-6

AII-14

H

OH

H

A2-7

AII-15

H

OH

A2-1

AII-16

H

OH

A2-2

AII-17

H

OH

A2-3

AII-18

H

OH

A2-4

AII-19

H

OH

A2-5

AII-20

H

OH

A2-6

AII-21

H

OH

A2-7

From the viewpoint of availability of the starting material, the compounds (AII-8) to (AII-14) are more preferable, and among them, the compound (AII-8) is more preferable.

The compound (IV) of the present invention can be produced, for example, by a method described in Japanese patent application laid-open No. 2002-363434, a method in which a compound represented by the formula (IV-1) is reacted with squaric acid (3, 4-dihydroxy-3-cyclobutene-1, 2-dione).

In the formula (IV-1), R ¹ 、R ² 、R ⁵ 、R ⁶ 、R ⁹ And Ar ¹ Each means the same as described above.

The amount of the squaric acid to be used is preferably 0.5 to 0.8 mol, and more preferably 0.55 to 0.6 mol, based on 1 mol of the compound represented by the formula (IV-I).

The reaction temperature is preferably 30-180 ℃, and more preferably 80-140 ℃. The reaction time is preferably 1 to 12 hours, and more preferably 3 to 8 hours.

From the viewpoint of yield, the reaction is preferably carried out in an organic solvent. Examples of the organic solvent include hydrocarbon solvents such as toluene and xylene; halogenated hydrocarbon solvents such as chlorobenzene, dichlorobenzene, chloroform and the like; alcohol solvents such as methanol, ethanol, isopropanol, butanol, etc.; nitrohydrocarbon solvents such as nitrobenzene; ketone solvents such as methyl isobutyl ketone; amide solvents such as 1-methyl-2-pyrrolidone, and the like, and these solvents may be used in combination. Among them, a mixed solvent of butanol and toluene is preferable. The amount of the organic solvent to be used is preferably 30 to 200 parts by mass, more preferably 50 to 150 parts by mass, based on 1 part by mass of the compound represented by the formula (IV-I).

The method for obtaining the compound (II) as the target compound from the reaction mixture is not particularly limited, and various known methods can be employed. For example, a method of filtering out precipitated crystals after cooling is exemplified. The filtered crystals are preferably washed with water or the like and then dried. Further, if necessary, the product may be further purified by a known method such as recrystallization.

The compound represented by the formula (IV-I) can be produced by reacting a compound represented by the formula (IV-2) with a compound represented by the formula (IV-3) to produce a compound represented by the formula (IV-4), and then reacting the compound represented by the formula (IV-4) with a compound represented by the formula (IV-5).

In the formulae (IV-2) to (IV-5), R ¹ 、R ² 、R ⁵ 、R ⁶ 、R ⁹ 、R ¹² And m each represents the same meaning as described above.

Examples of the method for producing the compound represented by the formula (IV-4) from the compound represented by the formula (IV-2) and the compound represented by the formula (IV-3) include various known methods, for example, the method described in Eur.J.org.chem.2012, 3105-3111.

Examples of the method for producing the compound represented by the formula (IV-1) from the compound represented by the formula (IV-4) and the compound represented by the formula (IV-5) include various known methods, for example, J.Polymer Science Part A: the method described in Polymer Chemistry 2012, 50, 3788-.

When the colorant (B) contains the 1 st dye (B-1), the content of the 1 st dye (B-1) is preferably 1 to 100% by mass, more preferably 3 to 99.9% by mass, based on the total amount of the colorant.

(the 2 nd dye)

The 2 nd dye (B-2) is only a squaric acid

There is no limitation to the dyes other than the dye,examples of The dye include oil-soluble dyes, acid dyes, amine salts of acid dyes, sulfonamide derivatives of acid dyes, and The like, and examples thereof include compounds classified as dyes in The color index (published by The Society of Dyers and Colourists), and known dyes described in dyeing notes (chromo). Further, according to the chemical structure, coumarin dyes, auriferous azo dyes, pyridone azo dyes, barbituric azo dyes, quinophthalone dyes, methine dyes, cyanine dyes, anthraquinone dyes, triphenylmethane dyes, xanthene dyes, phthalocyanine dyes, and the like can be given. These dyes may be used alone or in combination of 2 or more.

Specifically, c.i. solvent yellow 4 (hereinafter, the description of c.i. solvent yellow is omitted and only the number is described), 14, 15, 23, 24, 38, 62, 63, 68, 82, 94, 98, 99, 162;

c.i. solvent dyes such as c.i. solvent orange 2, 7, 11, 15, 26, 56,

c.i. acid yellow 1,3, 7, 9, 11, 17, 23, 25, 29, 34, 36, 38, 40, 42, 54, 65, 72, 73, 76, 79, 98, 99, 111, 112, 113, 114, 116, 119, 123, 128, 134, 135, 138, 139, 140, 144, 150, 155, 157, 160, 161, 163, 168, 169, 172, 177, 178, 179, 184, 190, 193, 196, 197, 199, 202, 203, 204, 205, 207, 212, 214, 220, 221, 228, 230, 232, 235, 238, 240, 242, 243, 251;

c.i. acid dyes such as c.i. acid orange 6, 7, 8, 10, 12, 26, 50, 51, 52, 56, 62, 63, 64, 74, 75, 94, 95, 107, 108, 169, 173, etc.,

c.i. direct yellow 2, 33, 34, 35, 38, 39, 43, 47, 50, 54, 58, 68, 69, 70, 71, 86, 93, 94, 95, 98, 102, 108, 109, 129, 136, 138, 141;

c.i. direct dyes such as c.i. direct orange 34, 39, 41, 46, 50, 52, 56, 57, 61, 64, 65, 68, 70, 96, 97, 106, 107, etc.,

c.i. mordant yellow 5, 8, 10, 16, 20, 26, 30, 31, 33, 42, 43, 45, 56, 61, 62, 65;

c.i. mordant dyes such as c.i. mordant oranges 3,4,5, 8, 12, 13, 14, 20, 21, 23, 24, 28, 29, 32, 34, 35, 36, 37, 42, 43, 47, 48, and the like.

As the 2 nd dye (B-2), yellow dyes such as coumarin dye, gold-containing azo dye, pyridone azo dye, barbiturate azo dye, quinophthalone dye, methine dye, and cyanine dye are preferable. The inclusion of a yellow dye is preferable because the brightness of the color filter can be improved.

Examples of the yellow dye include the following compounds.

When the 2 nd dye (B-2) is contained in the colorant (B) of the colored resin composition, the content of the 2 nd dye (B-2) is 3 to 99% by mass, preferably 4 to 98% by mass, based on the total amount of the colorants. If the 2 nd dye (B-2) is within the above range, the color value can be easily adjusted, and therefore, it is preferable. Further, it is preferable to contain a yellow dye as the 2 nd dye (B-2) and the content of the yellow dye is in the above range because the brightness in the case of producing a color filter can be improved.

(other colorant Components)

The coloring resin composition colorant (B) may contain a pigment (P) in addition to the 1 st dye (B-1) and the 2 nd dye (B-2) for toning, i.e., for adjusting spectral characteristics.

The pigment (P) is not particularly limited, and known pigments can be used, and examples thereof include pigments classified as pigments in The color index (published by The Society of Dyers and Colourists).

Examples thereof include yellow pigments such as c.i. pigment yellow 1,3, 12, 13, 14, 15, 16, 17, 20, 24, 31, 53, 83, 86, 93, 94, 109, 110, 117, 125, 128, 137, 138, 139, 147, 148, 150, 153, 154, 166, 173, 194, 214;

orange pigments such as c.i. pigment orange 13, 31, 36, 38, 40, 42, 43, 51, 55, 59, 61, 64, 65, 71, 73;

c.i. pigment green 7, 36, 58, etc.

The pigment (P) is preferably a yellow pigment such as c.i. pigment yellow 1,3, 12, 13, 14, 15, 16, 17, 20, 24, 31, 53, 83, 86, 93, 94, 109, 110, 117, 125, 128, 137, 138, 139, 147, 148, 150, 153, 154, 166, 173, 194, 214; and

green pigments such as c.i. pigment green 7, 36, 58,

more preferred are c.i. pigment yellow 150, 185 and c.i. pigment green 58.

The content of the colorant (B) is preferably 0.1 to 60% by mass, more preferably 1 to 55% by mass, and still more preferably 2 to 50% by mass, based on the total amount of solid components in the colored resin composition. When the content of the colorant (B) is within the above range, the color density at the time of producing a color filter is sufficient and a necessary amount of the copolymer (A) can be contained in the composition, and therefore, a color filter having sufficient mechanical strength can be formed. The "total amount of solid content" in the present specification means an amount obtained by removing the content of the solvent from the total amount of the colored resin composition. The total amount of the solid components and the content of each component relative to the total amount of the solid components can be measured by a known analytical means such as liquid chromatography or gas chromatography.

< polymerizable Compound (C) >)

The polymerizable compound (C) is a compound which can be polymerized by an active radical and/or an acid generated by the polymerization initiator (D), and examples thereof include a compound having a polymerizable ethylenically unsaturated bond, and a (meth) acrylate compound is preferable.

Among them, the polymerizable compound (C) is preferably a polymerizable compound having 3 or more ethylenically unsaturated bonds. Examples of such polymerizable compounds include trimethylolpropane tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, tripentaerythritol octa (meth) acrylate, tripentaerythritol hepta (meth) acrylate, tetrapentaerythritol deca (meth) acrylate, tetrapentaerythritol nona (meth) acrylate, tris (2- (meth) acryloyloxyethyl) isocyanurate, ethylene glycol-modified pentaerythritol tetra (meth) acrylate, ethylene glycol-modified dipentaerythritol hexa (meth) acrylate, propylene glycol-modified pentaerythritol tetra (meth) acrylate, propylene glycol-modified dipentaerythritol hexa (meth) acrylate, caprolactone-modified pentaerythritol tetra (meth) acrylate, and mixtures thereof, Caprolactone-modified dipentaerythritol hexa (meth) acrylate, and the like.

Among them, dipentaerythritol penta (meth) acrylate and dipentaerythritol hexa (meth) acrylate are preferable.

The weight average molecular weight of the polymerizable compound (C) is preferably 150 to 2900, and more preferably 250 to 1500.

The colored resin composition of the present invention may or may not contain the polymerizable compound (C). When the polymerizable compound (C) is contained, it is 50 parts by mass or less, preferably 30 parts by mass or less, and more preferably 10 parts by mass or less, per 100 parts by mass of the copolymer (a). When the content of the polymerizable compound (C) is within the above range, a colored resin composition capable of producing a coating film having more excellent solvent resistance can be obtained.

< polymerization initiator (D) >)

The polymerization initiator (D) is not particularly limited as long as it is a compound capable of initiating polymerization by generating an active radical, an acid, or the like by the action of light or heat, and a known polymerization initiator can be used. Examples of the polymerization initiator generating active radicals include an O-acyloxime compound, an alkylphenone compound, a triazine compound, an acylphosphine oxide compound, and a bisimidazole compound.

Examples of the O-acyloxime compound include N-benzoyloxy-1- (4-phenylsulfanylphenyl) butane-1-one-2-imine, N-benzoyloxy-1- (4-phenylsulfanylphenyl) octane-1-one-2-imine, N-benzoyloxy-1- (4-phenylsulfanylphenyl) -3-cyclopentylpropane-1-one-2-imine, N-acetoxy-1- [ 9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl ] ethane-1-imine, N-acetoxy-1- [ 9-ethyl-6- { 2-methyl-4- (3, 3-dimethyl-2, 4-dioxocyclopentylmethoxy) benzoyl } -9H-carbazol-3-yl ] ethane-1-imine, and N-acetoxy-1- [ 9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl ] -3-cyclopentylpropane-imine 1-imine, N-benzoyloxy-1- [ 9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl ] -3-cyclopentylpropane-1-one-2-imine. Commercially available products such as Irgacure (registered trademark) OXE01, OXE02 (manufactured by BASF Co., Ltd.), N-1919 (manufactured by ADEKA Co., Ltd.) and the like can also be used. Among them, the O-acyloxime compound is preferably at least one selected from the group consisting of N-benzoyloxy-1- (4-phenylsulfanylphenyl) butan-1-one-2-imine, N-benzoyloxy-1- (4-phenylsulfanylphenyl) octan-1-one-2-imine and N-benzoyloxy-1- (4-phenylsulfanylphenyl) -3-cyclopentylpropane-1-one-2-imine, and more preferably N-benzoyloxy-1- (4-phenylsulfanylphenyl) octan-1-one-2-imine. When these O-acyloxime compounds are used, a color filter having high luminance tends to be obtained.

Examples of the above-mentioned alkylphenone compound include 2-methyl-2-morpholino-1- (4-methylsulfanylphenyl) propan-1-one, 2-dimethylamino-1- (4-morpholinophenyl) -2-benzylbutan-1-one, 2- (dimethylamino) -2- [ (4-methylphenyl) methyl ] -1- [ 4- (4-morpholino) phenyl ] butan-1-one, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 2-hydroxy-2-methyl-1- [ 4- (2-hydroxyethoxy) phenyl ] propan-1-one, 1-hydroxycyclohexylphenyl ketone, oligomers of 2-hydroxy-2-methyl-1- (4-isopropenylphenyl) propan-1-one, α -diethoxyacetophenone, benzildimethylketal, and the like. Commercially available products such as Irgacure (registered trademark) 369, 907, and 379 (manufactured by BASF) may also be used.

Examples of the triazine compound include 2, 4-bis (trichloromethyl) -6- (4-methoxyphenyl) -1, 3, 5-triazine, 2, 4-bis (trichloromethyl) -6- (4-methoxynaphthyl) -1, 3, 5-triazine, 2, 4-bis (trichloromethyl) -6-piperonyl-1, 3, 5-triazine, 2, 4-bis (trichloromethyl) -6- (4-methoxystyryl) -1, 3, 5-triazine, 2, 4-bis (trichloromethyl) -6- [ 2- (5-methylfuran-2-yl) vinyl ] -1, 3, 5-triazine, 2, 4-bis (trichloromethyl) -6- [ 2- (furan-2-yl) vinyl ] -1, 3, 5-triazine, 2, 4-bis (trichloromethyl) -6- [ 2- (4-diethylamino-2-methylphenyl) vinyl ] -1, 3, 5-triazine, 2, 4-bis (trichloromethyl) -6- [ 2- (3, 4-dimethoxyphenyl) vinyl ] -1, 3, 5-triazine.

Examples of the acylphosphine oxide compound include 2,4, 6-trimethylbenzoyldiphenylphosphine oxide and the like. A commercially available product such as Irgacure (registered trademark) 819 (manufactured by BASF) may be used.

Examples of the biimidazole compound include 2,2 '-bis (2-chlorophenyl) -4, 4', 5,5 '-tetraphenylbiimidazole, 2' -bis (2, 3-dichlorophenyl) -4, 4 ', 5, 5' -tetraphenylbiimidazole (see, for example, japanese unexamined patent publication No. 6-75372, japanese unexamined patent publication No. 6-75373, etc.), 2 '-bis (2-chlorophenyl) -4, 4', 5,5 '-tetraphenylimidazole, 2' -bis (2-chlorophenyl) -4, 4 ', 5, 5' -tetrakis (alkoxyphenyl) biimidazole, 2 '-bis (2-chlorophenyl) -4, 4', 5,5 '-tetrakis (dialkoxyphenyl) biimidazole, 2' -bis (2-chlorophenyl) -4, 4 ', 5, 5' -tetrakis (trialkoxyphenyl) biimidazole (see, for example, japanese unexamined patent publication No. sho 48-38403, Japanese patent laid-open publication No. S62-174204, etc.), and bisimidazole compounds in which the phenyl group at the 4,4 ', 5, 5' -position is substituted with an alkoxycarbonyl group (see, for example, Japanese patent laid-open publication No. 7-10913, etc.).

Further, examples of the polymerization initiator (D) include benzoin compounds such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, and benzoin isobutyl ether; benzophenone compounds such as benzophenone, methyl o-benzoylbenzoate, 4-phenylbenzophenone, 4-benzoyl-4 ' -methyldiphenylsulfide, 3 ', 4,4 ' -tetrakis (t-butylperoxycarbonyl) benzophenone, and 2,4, 6-trimethylbenzophenone; quinone compounds such as 9, 10-phenanthrenequinone, 2-ethylanthraquinone, camphorquinone, etc.; 10-butyl-2-chloroacridone, benzil, methyl phenylglyoxylate, titanocene compounds, and the like.

Examples of the polymerization initiator for generating an acid include 4-hydroxyphenyldimethylsulfonium p-toluenesulfonate, 4-hydroxyphenyldimethylsulfonium hexafluoroantimonate, 4-acetoxyphenyldimethylsulfonium p-toluenesulfonate, 4-acetoxyphenyl-methylbenzylsulfonium hexafluoroantimonate, triphenylsulfonium p-toluenesulfonate, triphenylsulfonium hexafluoroantimonate, diphenyliodonium

P-toluenesulfonate and diphenyliodine

Hexafluoroantimonate and the like

Salts, nitrobenzyl tosylates, benzoin tosylate and the like.

The colored resin composition of the present invention may or may not contain the polymerization initiator (D). When the polymerization initiator (D) is contained, it is 50 parts by mass or less, preferably 30 parts by mass or less, and more preferably 10 parts by mass or less, per 100 parts by mass of the copolymer (a). When the content of the polymerization initiator (D) is within the above range, a colored resin composition capable of producing a coating film having more excellent solvent resistance can be obtained.

In the colored resin composition of the present invention, the total content of the polymerizable compound (C) and the polymerization initiator (D) is 50 parts by mass or less, preferably 30 parts by mass or less, and more preferably 10 parts by mass or less, per 100 parts by mass of the content of the copolymer (a). When the total content of the polymerizable compound (C) and the polymerization initiator (D) is within the above range, a colored resin composition having more excellent storage stability can be obtained. The colored resin composition of the present invention may not contain the polymerizable compound (C) and the polymerization initiator (D) at the same time.

< solvent (E) >

The solvent (E) is not particularly limited, and a solvent generally used in this field can be used. Examples thereof include an ester solvent (a solvent containing-COO-and not containing-O-in the molecule), an ether solvent (a solvent containing-O-and not containing-COO-in the molecule), an ether ester solvent (a solvent containing-COO-and not containing-O-in the molecule), a ketone solvent (a solvent containing-CO-and not containing-COO-in the molecule), an alcohol solvent (a solvent containing OH and not containing-O-, -CO-, and-COO-, a solvent), an aromatic hydrocarbon solvent, an amide solvent, and dimethyl sulfoxide.

Examples of the ester solvent include methyl lactate, ethyl lactate, butyl lactate, methyl 2-hydroxyisobutyrate, ethyl acetate, n-butyl acetate, isobutyl acetate, amyl formate, isoamyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, cyclohexanol acetate, and γ -butyrolactone.

Examples of the ether solvent include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, 3-methoxy-1-butanol, 3-methoxy-3-methylbutanol, tetrahydrofuran, tetrahydropyran, 1, 4-dibutylene glycol

Alkane, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, anisole, phenetole, methyl anisole, and the like.

Examples of the ether ester solvent include methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, methyl 2-methoxy-2-methylpropionate, ethyl 2-ethoxy-2-methylpropionate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, and the like.

Examples of the ketone solvent include 4-hydroxy-4-methyl-2-pentanone, acetone, 2-butanone, 2-heptanone, 3-heptanone, 4-methyl-2-pentanone, cyclopentanone, cyclohexanone, and isophorone.

Examples of the alcohol solvent include methanol, ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, propylene glycol, glycerin, and the like.

Examples of the aromatic hydrocarbon solvent include benzene, toluene, xylene, mesitylene, and the like.

Examples of the amide solvent include N, N-dimethylformamide, N-dimethylacetamide, and N-methylpyrrolidone.

Among the above solvents, organic solvents having a boiling point of 120 to 210 ℃ at 1atm are preferable from the viewpoint of coatability and drying property. As the solvent, propylene glycol monomethyl ether acetate, ethyl lactate, propylene glycol monomethyl ether, ethyl 3-ethoxypropionate, ethylene glycol monomethyl ether, diethylene glycol monoethyl ether, 4-hydroxy-4-methyl-2-pentanone, and N, N-dimethylformamide are preferable, and propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, N-dimethylformamide, N-methylpyrrolidone, and ethyl 3-ethoxypropionate are more preferable.

The content of the solvent (E) is preferably 70 to 95% by mass, and more preferably 75 to 92% by mass, based on the total amount of the colored resin composition of the present invention. In other words, the total amount of solid components in the colored resin composition is preferably 5 to 30% by mass, and more preferably 8 to 25% by mass. If the content of the solvent (E) is within the above range, flatness at the time of coating becomes good, and color density is not insufficient at the time of forming a color filter, and therefore, there is a tendency that display characteristics become good.

The content of the solvent (E) is preferably 70 to 95% by mass, and more preferably 75 to 92% by mass, based on the total amount of the colored resin composition of the present invention. In other words, the total amount of solid components in the colored resin composition is preferably 5 to 30% by mass, and more preferably 8 to 25% by mass. If the content of the solvent (E) is within the above range, the flatness at the time of coating tends to be good.

< polymerization initiation assistant (D1) >)

The polymerization initiation aid (D1) is a compound for accelerating the polymerization of the polymerizable compound whose polymerization is initiated by the polymerization initiator, or a sensitizer. The polymerization initiation assistant (D1) is usually used in combination with the polymerization initiator (D).

Examples of the polymerization initiation aid (D1) include amine compounds, alkoxyanthracene compounds, thioxanthone compounds, and carboxylic acid compounds.

Examples of the amine compound include alkanolamines such as triethanolamine, methyldiethanolamine, triisopropanolamine and the like; aminobenzoate such as methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, 2-dimethylaminoethyl benzoate and 2-ethylhexyl 4-dimethylaminobenzoate; and alkylamino benzophenones such as N, N-dimethyl-p-toluidine, 4 ' -bis (dimethylamino) benzophenone (known as michler's ketone), 4 ' -bis (diethylamino) benzophenone, and 4,4 ' -bis (ethylmethylamino) benzophenone, and among them, alkylamino benzophenones are preferable, and 4,4 ' -bis (diethylamino) benzophenone is preferable. Commercially available products such as EAB-F (manufactured by Baotai chemical Co., Ltd.) can also be used.

Examples of the alkoxyanthracene compound include 9, 10-dimethoxyanthracene, 2-ethyl-9, 10-dimethoxyanthracene, 9, 10-diethoxyanthracene, 2-ethyl-9, 10-diethoxyanthracene, 9, 10-dibutoxyanthracene, and 2-ethyl-9, 10-dibutoxyanthracene.

Examples of the thioxanthone compound include 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2, 4-diethylthioxanthone, 2, 4-dichlorothioxanthone, and 1-chloro-4-propoxythioxanthone.

Examples of the carboxylic acid compound include phenylsulfanylacetic acid, methylphenylsulfanylacetic acid, ethylphenylsulfanylacetic acid, methylethylphenylsulfanylacetic acid, dimethylphenylsulfanylacetic acid, methoxyphenylsulfanylacetic acid, dimethoxyphenylsulfanylacetic acid, chlorophenylsulfanylacetic acid, dichlorophenylsulfanylacetic acid, N-phenylglycine, phenoxyacetic acid, naphthylthioacetic acid, N-naphthylglycine, naphthyloxyacetic acid and the like.

When these polymerization initiation aids (D1) are used, the content thereof is 100 parts by mass or less per 100 parts by mass of the content of the polymerization initiator (D).

< leveling agent (F) >

Examples of the leveling agent (F) include a silicone surfactant, a fluorine surfactant, and a silicone surfactant having a fluorine atom. They may have a polymerizable group in a side chain.

Examples of the silicone surfactant include surfactants having a siloxane bond in the molecule. Specifically, Toray Silicone DC3PA, Toray Silicone SH7PA, Toray Silicone DC11PA, Toray Silicone SH21PA, Toray Silicone SH28PA, Toray Silicone SH29PA, Toray Silicone SH30PA, Toray Silicone SH8400 (manufactured by Toray Dow Corning Co., Ltd.), KP321, KP322, KP323, KP324, KP326, KP340, KP341 (manufactured by shin-Etsu chemical Co., Ltd.), TSF400, TSF401, TSF410, TSF4300, TSF4440, TSF4445, TSF-4446, TSF4452 and TSF4460 (manufactured by Momentive Performance Materials Japan contract Co., Ltd.) may be mentioned.

Examples of the fluorine-based surfactant include surfactants having a fluorocarbon chain in the molecule. Specifically, examples thereof include Fluorad (registered trademark) FC430, Fluorad FC431 (manufactured by Sumitomo 3M Co., Ltd.), Megafac (registered trademark) F142D, Megafac F171, Megafac F172, Megafac F173, Megafac F177, Megafac F183, Megafac F554, Megafac R30, Megafac RS-718-K (manufactured by DIC Co., Ltd.), Eftop (registered trademark) EF301, Eftop EF303, Eftop EF351, Eftop EF352 (manufactured by Mitsubishi electro Chemical Co., Ltd.), Surflon (registered trademark) S381, Surflon S382, Surflon SC101, Surflon SC105 (manufactured by Asahi Nitro Chemical Co., Ltd.), and E5844 (research by Daikne Chemical).

Examples of the silicone surfactant having a fluorine atom include surfactants having a siloxane bond and a fluorocarbon chain in the molecule. Specifically, Megafac (registered trademark) R08, Megafac BL20, Megafac F475, Megafac F477, and Megafac F443 (available from DIC) are mentioned.

The content of the leveling agent (F) is preferably 0.001 to 0.2 parts by mass, preferably 0.002 to 0.1 parts by mass, and more preferably 0.005 to 0.05 parts by mass, relative to 100 parts by mass of the content of the copolymer (a). If the content of the leveling agent (F) is within the above range, the flatness of the color filter can be improved.

< other coloring resin composition component >

The colored resin composition of the present invention may contain, as required, additives known in the art, such as fillers, other polymer compounds, adhesion promoters, antioxidants, light stabilizers, chain transfer agents, and the like.

< method for producing colored resin composition >

The colored resin composition of the present invention can be prepared, for example, by mixing the copolymer (a), the colorant (B), the solvent (E), and, if necessary, the polymerizable compound (C), the polymerization initiator (D), the leveling agent (F), the polymerization initiation aid (D1), and other components.

When the pigment (P) is contained, the pigment (P) is preferably mixed with a part or the whole of the solvent (E) in advance, and dispersed by using a bead mill or the like until the average particle diameter of the pigment becomes about 0.2 μm or less. In this case, a part or all of the pigment dispersant and the copolymer (A) may be blended as necessary. The remaining components are mixed into the pigment dispersion liquid thus obtained to have a predetermined concentration, whereby the target colored resin composition can be prepared.

The dyes may be dissolved in a part or the whole of the solvent (E) separately in advance to prepare a solution. The solution is preferably filtered by a filter having a pore size of about 0.01 to 1 μm.

The mixed colored resin composition is preferably filtered by a filter having a pore size of about 0.1 to 10 μm.

< method for manufacturing color filter >

Examples of the method for producing a color filter from the colored resin composition of the present invention include a method in which a substrate is coated with the colored resin composition, and then dried by heating (prebaking) and/or drying under reduced pressure to remove volatile components such as a solvent and dry the composition to form a smooth colored composition layer, followed by postbaking. The cured film, i.e., the colored coating film formed in this way may be the color filter of the present invention.

As the substrate, a glass plate such as quartz glass, borosilicate glass, alumina silicate glass, soda-lime glass having a silica-coated surface, a resin plate such as polycarbonate, polymethyl methacrylate, or polyethylene terephthalate, a substrate of silicon, a substrate having a thin film of aluminum, silver/copper/palladium alloy formed on the substrate, or the like can be used. Other color filter layers, resin layers, transistors, circuits, and the like may be formed on these substrates.

Examples of the coating method include spin coating, slit and spin coating.

The temperature for heating and drying is preferably 30 to 120 ℃, and more preferably 50 to 110 ℃. The heating time is preferably 10 seconds to 60 minutes, and more preferably 30 seconds to 30 minutes.

When the drying is carried out under reduced pressure, the drying is preferably carried out under a pressure of 50 to 150Pa and at a temperature of 20 to 25 ℃.

The film thickness of the colored resin composition is not particularly limited, and may be appropriately selected according to the film thickness of the target color filter.

Further, the film of the obtained colored resin composition is preferably post-baked. The post-baking temperature is preferably 150-250 ℃, and more preferably 160-235 ℃. The post-baking time is preferably 1 to 120 minutes, and more preferably 10 to 60 minutes.

The film thickness of the color filter obtained is not particularly limited, and can be suitably adjusted according to the purpose, use, and the like, and is, for example, 0.1 to 30 μm, preferably 0.1 to 20 μm, and more preferably 0.5 to 6 μm.

The cured coating film thus obtained may be patterned by, for example, etching.

The colored pattern can be produced by photolithography, ink jet printing, or the like using the colored resin composition of the present invention. Among them, when the colored resin composition contains the polymerizable compound (C) and the polymerization initiator (D), the photolithography method is preferable. The photolithography method is a method in which the colored resin composition is applied to a substrate, dried to form a colored composition layer, and the colored composition layer is exposed to light through a photomask and developed. The coating and drying can be carried out under the above conditions.

The colored composition layer is exposed through a photomask for forming a target colored pattern. The pattern on the mask is not particularly limited, and a pattern corresponding to the intended use may be used.

The light source used for exposure is preferably a light source that generates light having a wavelength of 250 to 450 nm. For example, light of less than 350nm may be cut off by a filter for cutting off the wavelength region, or light of around 436nm, 408nm, or 365nm may be selectively extracted by a band-pass filter for extracting the wavelength region. Specifically, mercury lamps, light emitting diodes, metal halide lamps, halogen lamps, and the like can be given.

In order to uniformly irradiate the entire exposure surface with parallel light rays or to perform precise alignment of the photomask and the substrate on which the colored composition layer is formed, it is preferable to use an exposure apparatus such as a mask aligner or a stepper.

The exposed colored composition layer is brought into contact with a developer to develop the colored composition layer, thereby forming a colored pattern on the substrate. By the development, the unexposed portion of the colored composition layer is dissolved in the developer and removed. The developer is preferably an aqueous solution of an alkaline compound such as potassium hydroxide, sodium bicarbonate, sodium carbonate, or tetramethylammonium hydroxide. The concentration of these basic compounds in the aqueous solution is preferably 0.01 to 10% by mass, more preferably 0.03 to 5% by mass. Further, the developer may contain a surfactant.

The developing method may be any of a paddle method, a dipping method, a spraying method, and the like. Further, the substrate may be inclined at an arbitrary angle during development.

After development, washing with water is preferably performed.

The resulting colored pattern is preferably post-baked. The post-bake temperature and time may be the same as those described above.

The colored resin composition of the present invention is useful for the production of color filters because it can produce a coating film having excellent solvent resistance. The color filter is useful as a color filter used in a display device (for example, a liquid crystal display device, an organic EL device, electronic paper, or the like) or a solid-state imaging device.

Examples

The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to these examples. In the examples, the% and parts of the contents and the amounts used are based on mass unless otherwise specified.

In the following synthesis examples, the structure of the compound was identified by NMR (JNM-EX-270; manufactured by Nippon electronics Co., Ltd.).

< Synthesis example 1: synthesis of copolymer a1 >

An appropriate amount of nitrogen was passed through a flask equipped with a reflux condenser, a dropping funnel and a stirrer, and replaced with a nitrogen atmosphere, 290 parts of propylene glycol monomethyl ether acetate was placed therein, and the mixture was heated to 85 ℃ while stirring. Subsequently, acrylic acid 3, 4-epoxytricyclo [5.2.1.0 ] was added dropwise over 4 hours ^2,6 ]Decan-8-yl ester and acrylic acid 3, 4-epoxytricyclo [5.2.1.0 ^2,6 ]A mixed solution of 94 parts of a mixture of decane-9-yl ester (containing the components in a ratio of 1: 1), 61 parts of 4-vinylbenzoic acid, 157 parts of phenyl methacrylate and 250 parts of propylene glycol monomethyl ether acetate.

On the other hand, a mixed solution prepared by dissolving 9 parts of 2, 2-azobis (2, 4-dimethylvaleronitrile) in 110 parts of propylene glycol monomethyl ether acetate was added dropwise over 5 hours. After completion of the dropwise addition, the flask was held at 85 ℃ for 3 hours, and then cooled to room temperature to obtain a copolymer (copolymer a1) solution having a B-type viscosity (23 ℃) of 70mPas and a solid content of 28.2% by weight. The resulting copolymer a1 had a weight average molecular weight (Mw) of 17000 and a molecular weight distribution (Mw/Mn) of 2.23. The copolymer a1 has the structural units shown below.

The weight average molecular weight (Mw) and the number average molecular weight (Mn) of the copolymer a1 in terms of polystyrene were measured by GPC under the following conditions.

The device comprises the following steps: HLC-8120 GPC (manufactured by Tosoh corporation)

Column: TSK-GELG 2000HXL

Column temperature: 40 deg.C

Solvent: THF (tetrahydrofuran)

Flow rate: 1.0mL/min

Test liquid solid content concentration: 0.001 to 0.01% by mass

Injection amount: 50 μ L

A detector: RI (Ri)

Calibration standard substance: TSK STANDARD POLYSTYRENE F-40, F-4, F-288, A-2500, A-500 (manufactured by Tosoh Corp.)

The ratio (Mw/Mn) of the weight average molecular weight to the number average molecular weight in terms of polystyrene obtained above was defined as a molecular weight distribution. The same applies to the following copolymers a2, a3 and a 4.

< Synthesis example 2: synthesis of copolymer a2 >

An appropriate amount of nitrogen gas was introduced into a flask equipped with a reflux condenser, a dropping funnel and a stirrer, and the atmosphere was replaced with nitrogen gas, and 290 parts of propylene glycol monomethyl ether acetate was placed therein and heated to 85 ℃ with stirring. Subsequently, acrylic acid 3, 4-epoxytricyclo [5.2.1.0 ] was added dropwise over 4 hours ^2,6 ]Decan-8-yl ester and acrylic acid 3, 4-epoxytricyclo [5.2.1.0 ^2,6 ]A mixed solution of 60 parts of a mixture of decane-9-yl ester (content ratio: 1), 40 parts of 4-vinylbenzoic acid, 205 parts of phenyl methacrylate and 250 parts of propylene glycol monomethyl ether acetate.

On the other hand, a mixed solution of 9 parts of 2, 2-azobis (2, 4-dimethylvaleronitrile) dissolved in 110 parts of propylene glycol monomethyl ether acetate was added dropwise over 5 hours. After completion of the dropwise addition, the flask was held at 85 ℃ for 3 hours, and then cooled to room temperature to obtain a copolymer (copolymer a2) solution having a B-type viscosity (23 ℃) of 70mPas and a solid content of 28.2% by weight. The resulting copolymer a2 had a weight average molecular weight (Mw) of 17000 and a molecular weight distribution (Mw/Mn) of 2.23. The copolymer a2 has the same structural units as the copolymer a1 described above.

< Synthesis example 3: synthesis of copolymer a3 >

An appropriate amount of nitrogen was passed through a flask equipped with a reflux condenser, a dropping funnel and a stirrer, and replaced with a nitrogen atmosphere, 290 parts of propylene glycol monomethyl ether acetate was placed therein, and the mixture was heated to 85 ℃ while stirring. Subsequently, acrylic acid 3, 4-epoxytricyclo [5.2.1.0 ] was added dropwise over 4 hours ^2,6 ]Decan-8-yl ester and acrylic acid 3, 4-epoxytricyclo [5.2.1.0 ^2,6 ]A mixed solution of 115 parts of a mixture of decane-9-yl ester (content ratio: 1), 78 parts of 4-vinylbenzoic acid, 113 parts of phenyl methacrylate and 250 parts of propylene glycol monomethyl ether acetate.

On the other hand, a mixed solution of 9 parts of 2, 2-azobis (2, 4-dimethylvaleronitrile) dissolved in 110 parts of propylene glycol monomethyl ether acetate was added dropwise over 5 hours. After completion of the dropwise addition, the flask was held at 85 ℃ for 3 hours, and then cooled to room temperature to obtain a copolymer (copolymer a3) solution having a B-type viscosity (23 ℃) of 70mPas and a solid content of 24.5 wt%. The resulting copolymer a3 had a weight average molecular weight (Mw) of 16000 and a molecular weight distribution (Mw/Mn) of 2.40. The copolymer a3 has the same structural units as the copolymer a1 described above.

< Synthesis example 4: synthesis of copolymer a4 >

An appropriate amount of nitrogen was passed through a flask equipped with a reflux condenser, a dropping funnel and a stirrer, and replaced with a nitrogen atmosphere, and 283 parts of propylene glycol monomethyl ether acetate was placed therein and heated to 85 ℃ while stirring. Subsequently, acrylic acid 3, 4-epoxytricyclo [5.2.1.0 ] was added dropwise over 4 hours ^2,6 ]Decan-8-yl ester and acrylic acid 3, 4-epoxytricyclo [5.2.1.0 ^2,6 ]Decan-9-yl ester (containing ratio)The ratio is 1: 1) 93 parts of the mixture (A), 31 parts of acrylic acid, 83 parts of phenyl methacrylate and 240 parts of propylene glycol monomethyl ether acetate.

On the other hand, a mixed solution prepared by dissolving 9 parts of 2, 2-azobis (2, 4-dimethylvaleronitrile) in 110 parts of propylene glycol monomethyl ether acetate was added dropwise over 5 hours. After completion of the dropwise addition, the flask was held at 85 ℃ for 3 hours, and then cooled to room temperature to obtain a copolymer (copolymer a4) solution having a B-type viscosity (23 ℃) of 167mPas and a solid content of 28.2%. The resulting copolymer a4 had a weight average molecular weight (Mw) of 17000 and a molecular weight distribution (Mw/Mn) of 2.41. The copolymer a4 has the structural units shown below.

< Synthesis example 5: squaric acid

Synthesis of dye b1 >

10.0 parts of 2, 4-dimethylaniline (manufactured by Tokyo chemical industry Co., Ltd.), 17.0 parts of 2-ethylbromohexane (manufactured by Tokyo chemical industry Co., Ltd.), and 44.0 parts of tetrabutylammonium bromide (manufactured by photochemical industry Co., Ltd.) were mixed. The resulting mixture was stirred at 90 ℃ for 8 hours. After completion of the reaction, 50 parts of 10% sodium bicarbonate solution was added, 100 parts of ethyl acetate was added, and the aqueous layer was discarded. After washing with water and 10% hydrochloric acid was repeated 2 times, the solvent was distilled off. The resulting oil was dried under reduced pressure at 60 ℃ for 24 hours to obtain 9.3 parts of a compound represented by the following formula (d-1).

Process for producing compound represented by the formula (d-1) ¹ H-NMR (270MHz, delta values (ppm, TMS basis), DMSO-d 6)0.85(m,6H), 1.23-1.42 (br,8H),1.59(br,1H),2.04(s,3H),2.12(s,3H),2.91(d,2H),4.37(br,1H),6.38(d,1H),6.75(s,1H),6.77(d,1H)

3.0 parts of the compound represented by the formula (d-1) obtained above, 2.2 parts of 3-bromophenol (manufactured by Tokyo chemical industry Co., Ltd.), 0.015 part of palladium acetate, 3.2 parts of sodium tert-butoxide (manufactured by Tokyo chemical industry Co., Ltd.), 0.055 part of tri-tert-butylphosphine (manufactured by Tokyo chemical industry Co., Ltd.), and 25.6 parts of toluene were mixed and stirred at 100 ℃ for 15 hours. To the resulting mixture were added 30 parts of ethyl acetate, 100 parts of water and the aqueous layer was discarded. After repeating the washing with water 2 times, the solvent was distilled off. The residue was purified by silica gel chromatography (chloroform/hexane ═ 1/1), and the obtained oil was dried at 60 ℃ under reduced pressure for 24 hours to obtain 1.9 parts of a compound represented by the following formula (d-2).

Process for producing compound represented by the formula (d-2) ¹ H-NMR (270MHz, delta values (ppm, TMS basis), DMSO-d 6)0.85(m,6H), 1.23-1.42 (br,8H),1.55(br,1H),1.94(s,3H),2.27(s,3H),2.90(d,2H),6.37(d,1H),6.75(s,1H),6.76(d,1H), 6.92-7.14 (m,4H),8.93(s,1H)

4.4 parts of the compound represented by the formula (d-2), which was an intermediate obtained as described above, 0.8 part of 3, 4-dihydroxy-3-cyclobutene-1, 2-dione (manufactured by Tokyo chemical Co., Ltd.), 90.0 parts of 1-butanol and 60.0 parts of toluene were mixed. The resulting mixture was stirred at 125 ℃ for 3 hours while removing the generated water using a Dean-Stark tube. After completion of the reaction, the solvent was distilled off, 15 parts of acetic acid was added thereto, and the mixture was added dropwise to 100 parts of 18% saline solution, and the precipitated solid was filtered off. The filtered solid was washed with hexane. Drying the obtained solid at 60 deg.C under reduced pressure for 24 hr to obtain compound (squaric acid) represented by formula (AII-8)

Dye b1)4.9 parts.

Process for producing compound represented by the formula (AII-8) ¹ H-NMR (270MHz, delta values (ppm, TMS basis), DMSO-d 6)0.87(m,12H), 1.21-1.57 (m,16H),1.72(br,2H),2.05(s,6H),2.36(s,6H),3.37(br,2H),3.78(br,2H),6.00(br,4H), 6.97-7.12 (m,6H), 7.77-7.95 (m,2H),11.35(s,1H),12.06(s,1H)

< Synthesis example 6: synthesis of yellow dye b2 >

A compound represented by the following formula (yellow dye b2) was produced by a method for producing a compound represented by the formula (Ad 2-14) described in Japanese patent laid-open publication No. 2016-11419. The compound represented by the following formula is the same compound as the compound represented by the formula (Ad 2-14) of Japanese patent laid-open publication No. 2016-11419.

[ preparation of colored resin composition ]

The respective components were mixed so as to have the compositions shown in table 2 below, thereby obtaining colored resin compositions of examples 1 to 5 and comparative example 1. The compositions shown in table 2 are calculated as solid contents except for the solvent (E). The numerical values of the respective components shown in table 2 are parts by mass.

The components in table 2 are shown below.

Copolymer a 1: compound synthesized by Synthesis example 1

Copolymer a 2: compound synthesized by Synthesis example 2

Copolymer a 3: compound synthesized by Synthesis example 3

Copolymer a 4: compound synthesized by Synthesis example 4

Squaric acid

Dye b 1: compound synthesized by Synthesis example 5

Yellow dye b 2: compound synthesized by Synthesis example 6

Solvent e 1: propylene glycol monomethyl ether acetate

Leveling agent f 1: megafac (registered trademark) F554 (manufactured by DIC corporation)

[ formation of coating film ]

The colored resin compositions prepared in examples 1 to 5 and comparative example 1 were applied to a 5cm square glass substrate (eagle XG; manufactured by Corning Corp.) by spin coating so that the film thickness after the post-baking became 0.5. mu.m, and then pre-baked on a hot plate at 70 ℃ for 1 minute to obtain a colored coating film. Then, the resultant was post-baked on a hot plate at 240 ℃ for 9 minutes to obtain a colored coating film (hereinafter referred to as "post-baked colored coating film").

< evaluation of solvent resistance >

5ml of a solvent (propylene glycol monomethyl ether acetate (PGMEA)) was dropped onto the colored coating film after the post-baking and left for 1 minute, and then the solvent was evaporated by drying. Then, the transmittance T of the colored coating film before the solvent dropping was measured with respect to light having a wavelength of λ (nm) _λ (%) and transmittance T 'of the colored coating film after drying after dropping the solvent' _λ (%). The transmittance was measured using a spectrophotometer (ultraviolet-visible near-infrared spectrophotometer V-770, manufactured by japan spectrofluorid). Scanning wavelength λ (nm) every 1nm in the range of 401-700 nm, that is, measuring at 300 points of 401nm, 402nm, 403nm, and … 700nm, and using the transmittance T at 300 points _λ And transmittance T' _λ The average transmittance change amount Δ T is calculated by the following equation. The calculation results are shown in table 2.

[ Table 2]

As shown in Table 2, the coating films of examples 1 to 5 using the colored resin composition containing the copolymer of the present invention have a smaller average change in transmittance due to dropping of the solvent than the coating film of comparative example 1.

Claims

1. A copolymer comprising a structural unit (Aa) derived from an aromatic carboxylic acid having an ethylenically unsaturated bond, a structural unit (Ab) represented by the formula (Z), and a structural unit (Ac) derived from an unsaturated compound having a cyclic ether structure having 2 to 4 carbon atoms,

in the formula (Z), L represents a linking group having a valence of 2, A represents a phenyl group which may have a substituent other than a carboxyl group or a naphthyl group which may have a substituent other than a carboxyl group, and R ^a Represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, wherein the hydrogen atom contained in the alkyl group may be substituted with a hydroxyl group,

the copolymer has 5 to 40 mol% of a structural unit (Aa), 5 to 90 mol% of a structural unit (Ab), and 5 to 40 mol% of a structural unit (Ac), based on the total structural units constituting the copolymer.

2. The copolymer according to claim 1, wherein the total content of the structural unit (Aa) and the structural unit (Ab) is 40 to 90 mol% based on the total amount of all the structural units.

3. A colored resin composition comprising the copolymer according to claim 1 or 2 and a colorant.

4. The colored resin composition according to claim 3, wherein the colorant contains a1 st dye, and the 1 st dye is a squarylium acid

A dye.

5. A cured film formed from the colored resin composition according to claim 3 or 4.

6. A color filter formed from the colored resin composition according to claim 3 or 4.